Cosmetic composition based on nanoparticles and on water-soluble organic silicon compounds

ABSTRACT

The invention concerns a composition comprising, in a cosmetically acceptable medium containing water and/or a solvent, metal, metal oxide, metal carbide or nitride nanoparticles or mixtures thereof, and one or several organic silicon compounds soluble in water and/or in the solvent, having one, two or three silicon atoms, and at least two hydroxyl or hydrolysable groups per molecule. The invention is applicable to hair care compositions.

This application is the U.S. national phase of international applicationPCT/FR01/00952 filed 29 Mar. 2001, which designated the U.S.

The present invention relates generally to aqueous cosmeticcompositions, in particular for treating the hair, comprisingnanoparticles and water-soluble organosilicon compounds.

Styling products exist which are used for increasing the volume of thehairstyle. These products, based on film-forming polymers, areparticularly appreciated by users with fine hair.

These styling products leave a somewhat unnatural feel resulting fromthe deposition of polymer on the surface of the hair.

It is moreover possible to use permanent-waving treatments. Thesetreatments, based on the use of a reducing agent and an oxidizing agent,require the hair to be placed under mechanical tension by means ofrolling equipment, to give the head of hair a long-lasting shape. Thisprocess does indeed make it possible to increase the volume of the headof hair. However, these treatments have the drawback of modifying theappearance of the hair (curly hair) and of degrading the condition ofthe fibers.

No treatment exists for increasing the volume of the head of hairwithout modifying the shape or feel of the hair.

It has now been discovered, surprisingly, that it is possible toincrease the volume of the head of hair without modifying the shape orfeel of the hair, by using specific compositions described below.

With these compositions, the body of the hairstyle can be increased,without impairing the feel of the hair or its shape, without degradingthe fibers and without adhesion between the hairs by a film-formingmaterial.

Moreover, it has also been found that the use of these compositionsmakes the hair feel thicker (although the thickness of the hairs has notbeen increased). This observation is particularly advantageous sincemany users appreciate this sensation of fortified hair.

According to the invention, the compositions are characterized in thatthey contain, in a cosmetically acceptable medium comprising waterand/or at least one solvent, i) nanoparticles chosen from metallicnanoparticles, of metal oxides, of metal carbides or nitrides andmixtures thereof, and ii) one or more organosilicon compounds that aresoluble in the cosmetically acceptable medium, chosen from organosilanescomprising one, two or three silicon atoms and organosiloxanescomprising two or three silicon atoms, the silicon compounds alsocomprising two hydrolyzable or hydroxyl groups per molecule.

The term “nanoparticles” means particles less than 200 nm and preferablyless than 50 nm in size.

Among the metal oxide nanoparticles that may be mentioned are ceriumoxide (CeO), alumina (Al₂O₃), titanium oxide (TiO₂), titanates (BaTiO₃,Ba_(0.5)Sr_(0.5)TiO₃, SrTiO₃), indium oxide (In₂O₃), tin oxide (SnO₂),antimony oxide (Sb₂O₃), magnesium oxide (MgO), calcium oxide (CaO),manganese oxides (Mn₃O₄, MnO₂), molybdenum oxide (MoO₃), silica (SiO₂),zinc oxide (ZnO), yttrium oxide (Y₂O₃), etc., and mixtures thereof.

Among the metallic nanoparticles that may be mentioned are nanoparticlesof silver, gold, platinum, indium, etc., and mixtures thereof.

Among the metal carbides and nitrides that may be mentioned are siliconcarbide (SiC) and silicon nitride (Si₃N₄).

Preferably, the nanoparticles are alumina nanoparticles.

The amount of nanoparticles in the compositions generally ranges from0.01% to 30% by weight and preferably from 0.05% to 5% by weight,relative to the total weight of the composition.

The second essential constituent of the compositions of the invention isthe silicon compound(s), which may be sparingly polymerized orunpolymerized, and soluble in the cosmetically acceptable medium andmore particularly in water and/or the solvent(s) of this medium.

As mentioned previously, the organosilicon compounds are chosen fromorganosilanes that are soluble in water and/or solvents, comprising one,two or three silicon atoms, and organosiloxanes that are soluble inwater and/or solvents, comprising two or three silicon atoms, preferablytwo silicon atoms, these compounds also comprising at least twohydrolyzable or hydroxyl groups per molecule.

Preferably, the organosilicon compounds of the invention comprise threehydrolyzable and/or hydroxyl groups per molecule. The preferredhydrolyzable groups are chosen from alkoxy, aryloxy and halogen groups.

The organosilicon compound can bear one or more functions making itcompatible with water and/or solvents, and/or giving it affinity withkeratin fibers.

Preferably, the organosilicon compound bears one or more solubilizingfunctions, which in particular improve the solubility in water, forexample basic functions such as alkylamine and alkylpolyamine functions,and nonbasic functions such as alkyl alcohol, alkylthiol, alkyl acid,alkylpolyol and alkylpolycarboxylic functions.

Among the solubilizing functions, the preferred functions are basicfunctions, in particular primary, secondary and tertiary aminefunctions.

The basic chemical function(s) may be partially or totally neutralized,for example by adding to the composition a suitable amount of an acidsuch as hydrochloric acid, sulfuric acid or sulfuric acid salts, nitricacid and mono-, di- or tricarboxylic organic acids.

The preferred acids are sulfuric acid and its salts.

The organosilanes that are preferred according to the inventioncorrespond to the formula:

in which:

-   R₄ represents a halogen or a group OR′ or R′₁;-   R₅ represents a halogen or a group OR″ or R′₂;-   R₆ represents a halogen or a group OR′ or R′₃;-   and R₁, R₂, R₃, R′, R″, R″′, R′₁, R′₂ and R′₃ represent,    independently of each other, a saturated or unsaturated, linear or    branched hydrocarbon-based group optionally bearing additional    chemical groups such as acid or amine groups, R₁, R₂, R′, R″ and R″′    also possibly denoting hydrogen, and-   at least two of the groups R₄, R₅ and R₆ being other than groups    R′₁, R′₂ and R′₃.

Preferably, R₁, R₂, R′, R″ and R″′, R′₁, R′₂ and R′3 represent a C₁ toC₁₂ alkyl group, a C₅ to C₁₄ aryl group, a (C₁ to C₈) alkyl (C₅ to C₁₄)aryl group and a (C₅ to C₁₄) aryl (C₁ to C₈) alkyl group; and R₃ ispreferably a C₁ to C₁₂ alkylene group, a C₅ to C₁₄ arylene group, a (C₁to C₈) alkyl (C₅ to C₁₄) arylene group and a (C₅ to C₁₄) aryl (C₁ to C₈)alkylene group.

The organosiloxanes that are preferred in the compositions of thepresent invention may be represented by the formula:

in which:

-   R₁, R₂, R₃, R₅ and R₄ are defined as above;-   R′₄ represents a halogen or a group OR₁₁;-   R₇ represents a halogen or a group OR₁₀ or R″₁;-   R₉ represents a halogen or a group OR₈, R″₂ or R₃NR₁R₂;-   R″₁, R″₂, R₈, R₁₀ and R₁₁ represent a saturated or unsaturated,    linear or branched hydrocarbon-based group optionally bearing    additional chemical groups such as basic solubilizing groups;-   R₁₁, R₁₀ and R₈ also possibly denoting hydrogen.

Preferably, R″₁, R″₂, R₈ or R₁₀ and R₁₁ represent a C₁ to C₁₂ alkylgroup, a C₅ to C₁₄ aryl group, a (C₁ to C₈) alkyl (C₅ to C₁₄) aryl groupand a (C₅ to C₁₄) aryl (C₁ to C₈) alkyl group.

At least one of the groups R₆, R₇ and R₉ denotes a halogen or a groupOR″′, OR₁₀ or OR₈.

Preferably, the halogen is chlorine.

The organosilicon compounds that are preferred are3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane and3-[bis(hydroxyethyl)amino]propyltriethoxysilane.

The compound that is particularly preferred is3-aminopropyltriethoxysilane.

The amount of organosilicon compounds present in the compositiongenerally represents 0.1% to 50% and preferably 1% to 20% of the totalweight of the composition.

Preferably, the “nanoparticles/silicon compound” concentration ratio isfrom 0.05 to 2.

The content of organosilicon compounds according to the invention isdetermined by usual analytical methods such as 29-silicon and proton NMRspectroscopy, and by chromatography.

Although the compositions according to the invention are preferablyaqueous compositions, solvents and mixtures of solvents such as analcohol or a ketone, for example ethanol or acetone, may be used in thecompositions.

In a known manner, all the compositions of the invention may containadjuvants that are common in cosmetics, such as oils, waxes or otherusual fatty substances; standard gelling agents and/or thickeners;propenetrating agents; reducing agents; emulsifiers; moisturizers;emollients, sunscreens; softeners; hydrophilic or lipophilic activeagents, for instance ceramides; antifoams; antiperspirants; free-radicalscavengers; surfactants; fixing or nonfixing polymers; proteins;bactericides; sequestering agents; antidandruff agents; antioxidants;basifying agents; preserving agents; fragrances; fillers; dyestuffs suchas colorants and pigments; volatile or nonvolatile silicones; polyols;proteins and vitamins.

The amounts of these various adjuvants are those conventionally used inthe field under consideration.

Needless to say, a person skilled in the art will take care to selectthe optional compound(s) added to the composition according to theinvention such that the advantageous properties intrinsically associatedwith the composition in accordance with the invention are not, or arenot substantially, adversely affected by the envisaged addition.

The compositions according to the invention are preferably used inrinse-out mode, i.e. the compositions are applied to the hair and arethen left to stand for a few minutes or more before being rinsed out.

The compositions according to the invention may be in any form that issuitable for topical application, especially in the form of solutions oflotion or serum type; in the form of aqueous gels; in the form ofemulsions obtained by dispersing a fatty phase in an aqueous phase (O/W)or conversely (W/O), of more or less thick liquid consistency, such asmore or less unctuous milks or creams.

These compositions are prepared according to the usual methods.

The compositions according to the invention are preferably used as hairproducts, especially for holding the hairstyle or shaping the hair. Theymay also give the hair a temporary coloration, and may effectivelyensure protection of the hair against the effects of UV radiation, whileat the same time giving the hair holding or fixing properties.

The hair compositions according to the invention are preferably stylingproducts such as hairsetting shampoos, gels and lotions, blow-dryinglotions, and fixing and styling compositions such as lacquers or sprays.

The lotions may be packaged in various forms, especially in vaporizers,pump-dispenser bottles or in aerosol containers to allow an applicationof the composition in vaporized form or in the form of a mousse. Suchpackaging forms are indicated, for example, when it is desired to obtaina spray or a mousse for fixing or treating the hair.

The nanoparticles may also be introduced into the composition directlyat the time of use.

A subject of the present invention is also the use of the compositionaccording to the invention in a hair treatment process.

According to one embodiment of this process, the composition is appliedto the rinsed or unrinsed hair, preferably in the form of a spray,either using a pump-dispenser bottle or using an aerosol.

After spraying over the entire head of hair, the composition is left toact and to dry.

The hair is then rinsed with water.

The hair may be set in the desired shape, either before the applicationor immediately after.

The drying time may be variable and depends on the nature of thecomposition.

After combing, the hair has more body and a very pleasant feel.

The invention is illustrated by the following examples:

EXAMPLE 1

The four formulations below were prepared:

Aminopropyltri- Alumina ethoxysilane nanoparticles* Water Formulation(weight %) (weight %) (weight %) 1 12.5 0.5 87 Comparative A 12.5 — 87.5Comparative B — 0.5 99.5 Control — — 100 *Nanoparticles sold under thename “Nanotek ® aluminum oxide dispersion” by the company NanophaseTechnologies Corporation.

5 g of formulation 1 described above and 5 g of the comparativeformulation A are applied to two different heads of hair (Europeanchestnut-brown hair about 20 cm long) by spraying using a spray. Afterleaving to stand for 15 minutes, the hair is rinsed with water.

In order to show the hair volumizing effect generated by applying thevarious preceding formulations, the change in the flexural rigidity ofthe hair after treatment of the fibers was measured by means of the“flexibility pendulum” method.

The pendulum used is of the rigid swing type with a one-second beat.This pendulum consists of a polished-brass bending bar. This bar isconnected to an axle via a rod of length L=30 cm. On this rod, at adistance L′=18.5 cm from the axis of rotation, is mounted a weighted barof mass m=47 g. The initial potential energy of the balance arm is setby its angle of inclination, written as θ.

The samples of hair are in the form of a comb of 39 fragments of hair 11mm long bonded in parallel onto a metal support.

The measurement is performed as follows: the brass bar is released at anangle θ=30° without initial speed. At each passage through the bottompoint (θ=0), the bar bends the sample of 39 hairs and loses some of itspotential energy, until it comes to a complete standstill. The fasterthe pendulum is stopped, the more rigid are the hairs. It is consideredthat the loss of energy associated with the friction of the brass bar onthe hairs is negligible.

To demonstrate the hair volumizing effect, a first measurement is takenbefore treatment, a second measurement is then taken after treatment andthe number of beats required to stop the pendulum before and aftertreatment is then compared.

The treatment of the hairs is performed directly on the hairs mounted onthe samples so as to obtain greater measurement sensitivity. For eachtreatment, a series of measurements is performed on 10 samples. Themeasurements and the drying of the samples of hair are performed atcontrolled temperature and relative humidity (20° C. and 45% RH).

Under the application conditions described above, it is noted that thevarious hair treatments induce a decrease in the number of beatsrequired to stop the pendulum.

The different percentages of variation in the number of beats of thependulum after application of the formulations described above arecollated in the table below.

Comparative Comparative Treatment Formulation 1 formulation Aformulation B % variation in the −15% ± 2% −6% ± 1% −10% ± 2% number ofbeats of the pendulum after treatment

This result shows that the application of alumina nanoparticles allowsthe hair to be rigidified. This explains the reduced bending of thefibers observed due to the effect of gravity, visualized by a moremarked volumizing of the head of hair. It is also noted that the fibervolumizing effect is increased when the nanoparticles are combined witha compound (comparative formulation B) of the type such as3-aminopropyltriethoxysilane.

A marked effect of reduced bending of the fibers due to the effect ofgravity during the use of formulation 1 compared with comparativeformulation A is noted. This phenomenon is reflected visually by a morepronouced volumizing of the hairstyle after this formulation is applied.This rigidification of the fiber is amplified during the use of theorganosilane. Specifically, formulation 1 gives the head of hair greatervolume than the comparative formulation B, which is itself moreeffective than the control.

1. A cosmetic composition comprising, in a cosmetically acceptablemedium including water and/or one or more solvents, i) from 0.05 to 5%by weight, relative to the weight of the composition, of nanoparticlesconsisting of metal oxide, and ii) from 1 to 20% by weight, relative tothe weight of the composition, of at least one organosilicon compoundthat is soluble in the cosmetically acceptable medium, theseorganosilicon compounds comprising at least two hydroxyl or hydrolyzablegroups per molecule and being chosen from the compounds of formulae:

in which: R₄ represents a halogen or a group OR′ or R′₁; R₅ represents ahalogen or a group OR″ or R′₂; R₆ represents a halogen or a group OR″′or R′₃; and R₁, R₂, R₃, R′, R″, R″′, R′₁, R′₂ and R′₃ representindependently of each other, a saturated or unsaturated, linear orbranched hydrocarbon-based group optionally bearing additional chemicalgroups, wherein R₁, R₂, R′, R″, and R′″ may possibly be hydrogen alsopossibly denoting hydrogen, at least two of the groups R₄, R₅ and R₆being other than groups R′₁, R′₂ and R′₃.
 2. The cosmetic composition asclaimed in claim 1, characterized in that the organosilicon compoundscomprise three hydrolyzable or hydroxyl groups per molecule.
 3. Thecosmetic composition as claimed in claim 1, characterized in that thegroups R₁, R₂, R′, R′₁, R′₂, R′₃, R″, R″′ are chosen from C₁₋₁₂ alkyl,C₅₋₁₄ aryl, (C₁₋₈ )alkyl(C₅₋₁₄ )aryl and (C₅-C₁₄)aryl(C₁₋₈ )alkylradicals.
 4. The composition as claimed in claim 1, wherein the metaloxide is selected from the group consisting of CeO, Al₂O₃, TiO₂, BaTiO₃,Ba_(0.5)Sr_(0.5)TiO₃, SrTiO₃, In₂O₃, SnO₂, Sb₂O₃, MgO, CaO, Mn₃O₄,Mn₃O₄, MnO₂, MoO₃, SiO₂, ZnO, and Y₂O₃.
 5. The composition as claimed inclaim 1, characterized in that the nanoparticles are less than 200 nm insize.
 6. The composition as claimed in claim 1, characterized in thatthe “monoparticles/organosilicon compound” concentration ratio rangesfrom 0.05 to 2.